Delustered thermoplastic resin composition

ABSTRACT

A delustered thermoplastic resin composition which comprises 100 parts by weight of a thermoplastic resin (B); and 0.1 to 40 parts by weight of a resin (A) which essentially consists of: 
     80 to 20 parts by weight of a polymer or a copolymer component (I) obtained by polymerizing; 
     (a) 30 to 100% by weight of at least one monomer selected from the group consisting of an alkyl methacrylate in which the alkyl group has 1 to 4 carbon atoms and an aromatic vinyl compound; 
     (b) 0 to 70% by weight of an alkyl acrylate in which the alkyl group has 1 to 13 carbon atoms; 
     (c) 0 to 50% by weight of a monoethylenically unsaturated monomer other than those of (a) and (b); and 
     (d) 0 to 5 parts by weight of a crosslinking monomer per 100 parts by weight of the total amount of the above components (a), (b), and (c); and 
      20 to 80 parts by weight of a copolymer component (II) obtained by polymerizing; 
     (e) 30 to 90% by weight of an aromatic vinyl compound; 
     (f) 10 to 60% by weight of at least one alkyl acrylate monomer in which the alkyl group has 1 to 13 carbon atoms; 
     (g) 0 to 20% by weight of a monoethylenically unsaturated monomer other than those of (e) and (f); and 
     (h) 0.05 to 10 parts by weight of a crosslinking monomer per 100 parts by weight of the total amount of the above components (e), (f) and (g).

CROSS REFERENCE TO RELATED APLICATIONS

This application is a continuation-in-part of application Ser. No.204,169 filed Nov. 5, 1980 now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a delustered thermoplastic resincomposition.

2. Description of the Prior Art

Molded products of thermoplastic resins such as of vinyl chloride resinand ABS resin have luster. Although the luster may serve as an importantproperty depending upon the purposes, it is often desired to eliminatethe luster.

In order to deluster the thermoplastic resins, it has heretofore beenattempted to perform the pattern embossing treatment and to perform thedelustering coating because they do not deteriorate the properties ofthe thermoplastic resins. These methods, however, require clumsy stepsas well as increased cost, while presenting such a problem that thedelustering effect does not last long.

It has also been attempted to add a delustering agent of the inorganictype of the high molecular polymer type. This method does not hinder theprocessability and gives the delustering effect which lasts for extendedperiods of time, but gives a serious defect that the properties of theresins become inferior. In particular, the inorganic delustering agentsuch as amorphous silica or calcium carbonate, which had been chieflyused as the delustering agent of the addition type, causes the physicalproperties of the resins to be worse and can not be practically used.

On the other hand, when the delustering agent of the high molecularpolymer type is used, it is possible to diminish a lowering of physicalproperties by using a delustering agent having a better compatibilitywith the resin. However, in such case, the delustering effect is oftendiminished because the compatibility with respect to the thermoplasticresin conflicts the delustering efect, and this conflicting nature ofthe compatibility and the delustering effect has prevented thedevelopment of excellent delustering agent.

SUMMARY OF THE INVENTION

The object of the present invention is to provide an excellentdelustering agent, physical properties of which are not substantiallydeteriorated and which can be commercially produced.

PREFERRED EMBODIMENT OF THE INVENTION

The present invention deals with a delustering thermoplastic resincomposition comprising 100 parts by weight of a thermoplastic resin (B)blended

with 0.1 to 40 parts by weight of a mixture (A₁) of a polymer or acopolymer (component I) from the below-mentioned monomers (a) to (d) anda copolymer (component II) from the below-mentioned monomers (e) to (h),

with 0.1 to 40 parts by weight of a copolymer (A₂) obtained bypolymerizing a mixture of the monomers (e) to (h) in the presence of apolymer or a copolymer (component I) from the monomers (a) to (d),

or with 0.1 to 40 parts by weight of a copolymer (A₃) obtained bypolymerizing the monomer (a) or a mixture of the monomers (a) to (d) inthe presence of the copolymer (component II) from monomers (e) to (h).

Monomers for component I:

    ______________________________________                                        (a)   At least one monomer                                                                              30-100% by weight                                         selected from the group                                                       consisting of an alkyl                                                        methacrylate in which the                                                     alkyl group has 1 to 4                                                        carbon atoms and an aromatic                                                  vinyl compound                                                          (b)   Alkyl acrylate in   0-70% by weight                                           which the alkyl group                                                         has 1 to 13 carbon                                                            atoms                                                                   (c)   Any other mono-     0-50% by weight                                           ethylenically                                                                 unsaturated monomer                                                     (d)   Crosslinking monomer                                                                              0-5 parts by weight                                                           per 100 parts by                                                              weight of (a), (b)                                                            and (c).                                            ______________________________________                                    

Monomers for component II:

    ______________________________________                                        (e)   Aromatic vinyl monomer                                                                            30-90% by weight                                    (f)   At least one alkyl  10-60% by weight                                          acrylate monomer in                                                           which the alkyl group                                                         has 1 to 13 carbon atoms                                                (g)   Any other monoethyl-                                                                              0-20% by weight                                           enically unsaturated                                                          monomer                                                                 (h)   Crosslinking monomer                                                                              0.05-10 parts by                                                              weight per 100                                                                parts by weight of                                                            (e), (f) and (g).                                   ______________________________________                                    

According to the present invention, the polymer or copolymer (componentI) part from monomers (a) to (d) and the copolymer (component II) partfrom monomers (e) to (h) are essential requirements. When eithercomponent I or II was used, sufficient delustering effect can not beobtained, of insufficient compatibility with the thermoplastic resin (B)causes the physical properties of the final product to be seriouslydeteriorated. The ratio of the component (I) to the component (II)should suitably lie from 80:20 to 20:80 on the basis of weight.

As explained above, suitable monomers for constituting the component (I)include 30 to 100% by weight of alkyl methacrylate in which the alkylgroup has 1 to 4 carbon atoms and/or aromatic vinyl monomer, 0 to 70% byweight of alkyl acrylate in which the alkyl group has 1 to 13 carbonatoms, and 0 to 50% by weight of any other monoethylenically unsaturatedmonomer. It is also allowable to use 5 parts by weight or less of acrosslinking monomer per 100 parts by weight of the above-mentionedmonomers.

The component (I) works to impart compatibility with the thermoplasticresin to the delustering agent. This can be accomplished by using atleast 30% by weight of alkyl methacrylate in which the alkyl group has 1to 4 carbon atoms and/or an aromatic vinyl monomer as represented bystyrene. There can also be used a crosslinking monomer. Use of thecrosslinking monomer in excess amounts, however, causes thecompatibility to be decreased. Therefore, the crosslinking monomershould be used in a minimum amount.

Suitable monomers for constituting the component (II) include 30 to 90%by weight of aromatic vinyl monomer, 10 to 60% by weight of an acrylateand 0 to 60% by weight of any other monoethylenically unsaturatedmonomer. Further, a crosslinking monomer is used in an amount of 0.05 to10 parts by weight per 100 parts by weight of these monomers. Thecomponent (II) is essential for delustering. A crosslinked polymer ofwhich the main components are aromatic vinyl and acrylate exhibits aparticularly excellent delustering effect. The component (II) alone,however, is insufficient in compatibility with the thermoplastic resinand does not help to obtain an excellent delustering agent, unless it isused in combination with the component (I).

Representative examples of the monoethylenically unsaturated monomerswhich can be included in the monomers for the component I or II will befumaric acid, maleic acid and carboxylic acid copolymerizable therewithas well as esters thereof, halogenated vinyl compound such as vinylchloride and vinyl bromide, vinyl esters such as vinyl acetate, andacrylonitriles.

The crosslinking monomer is not essential for the component (I) but isessential for the component (II). When the crosslinking monomer is notused in the component (II), sufficient delustering effect is notobtained. Any crosslinking monomer may be used such as ordinarilyemployed polyfunctional monomer, e.g., polyvinylbenzenes and esters ofunsaturated carboxylic acid. Particularly preferred examples will beallyl compounds such as allyl methacrylate, triallyl cyanurate, triallylisocyanurate, and the like.

A mixture (A₁) of the polymer or copolymer component (I) and thecopolymer component (II), a copolymer (A₂) formed by polymerizing amixture of the monomers for the component (II) in the presence of thecomponent (I), and a copolymer (A₃) formed by polymerizing the monomer(a) or a mixture of monomers (a) to (d) for the component (I) in thepresence of the copolymer component (II), can be obtained by using theemulsion polymerization, multistage emulsion polymerization, or by usingthe emulsion suspension polymerization in which the emulsionpolymerization is effected in the first stage and the thus formed latexis once softly coagulated and is then subjected to the suspensionpolymerization by adding monomers in the second stage. Thepolymerization method, however, need not necessarily be limited thereto.

In particular, when the resin obtained by the emulsion polymerization isadded to a plasticized vinyl chloride resin or the like, excellentdispersibility is exhibited as compared with other resins that areformed by other polymerization methods such as suspensionpolymerization.

When the resin A (A₁, A₂ or A₃) is to be obtained by the emulsionpolymerization, it has preferably an average particle size of greaterthan 0.1μ and, particularly greater tna 0.3μ to produce increased effectof delustering. Namely, greater particle size is preferred so far as thestability of the formed latex is not deteriorated.

In carrying out the polymerization to obtain the resin, it is allowableto use a polymerization regulator such as n-octyl mercaptan or t-dodecylmercaptan. In many cases, it is often preferable to adjust thedistribution of the molecular weight by using such a polymerizationregulator.

Representative examples of the thermoplastic resin which exhibits thedelustering effect when blended with the resin (A₁), the resin (A₂) orthe resin (A₃), include vinyl chloride resin, ABS resin, (meth)acrylicresin, methyl methacrylate/butadiene/styrene resin (MBS resin), nylon,polyethylene, polycarbonate, polyethylene terephthalate, and the like.

The delustering agent will be blended into the thermoplastic resin in anamount of 40 parts by weight or less per 100 parts by weight of thethermoplastic resin. The delustering effect, however, can besufficiently exhibited even when the delustering agent is blended in anamount of 10 parts by weight or less.

In addition, by blending such a delustering agent into the thermoplasticresin, the surface of the molded article obtained from the blend isnecessarily rough and, as the result, blocking between molded articlesis often prevented. Such an anti-blocking effect is notable in case ofplasticized or semirigid polyvinylchloride.

As required, the composition of the present invention can be blendedwith general additives such as stabilizers, lubricants, processing aids,impact resistance aids, plasticizers, foaming agents, fillers, coloringagents, and the like.

In the following examples, parts and % are all by weight.

EXAMPLE 1 (1) Preparation of the component (I)

250 Parts of water, monomers in parts shown in Table 1, 1 part of sodiumN-lauroyl sarcosinate and 0.3 part of potassium persulfate were fed intoa reaction vessel equipped with a stirrer, a reflux condenser and anopening for introducing nitrogen gas. After the interior of the vesselwas sufficiently substituted with nitrogen gas, the above-mentionedcomponents were heated at 70° C. for 4 hours to polymerize the monomerswith stirring to obtain latexes having a polymerization rate of about96%.

                  TABLE 1                                                         ______________________________________                                        Monomer       (I)-1    (I)-2  (I)-3 (I)-4                                                                              (I)'-1                               ______________________________________                                        Methyl methacrylate                                                                         100      80     80     0   20                                   Butyl acrylate                                                                              0        20     20    40   80                                   Styrene       0         0     0     60    0                                   Allyl methacrylate                                                                          0         0     0.5    0    0                                   ______________________________________                                    

Measurement by the light transmission method indicated that particles inthe latexes of (I)-1 to (I)-4 possessed particle diameters of 0.3 to 0.4micron. The latexes were salted out by the addition of 5 parts ofcalcium chloride, and were further dehydrated, washed with water andwere dried to obtain powdery polymers.

In the case of (I)'-1, on the other hand, the resulting productexhibited a rubbery state.

(2) Preparation of the component (II)

250 Parts of water, monomers in parts shown in Table 2, 1 part of sodiumN-lauroyl sarcosinate and 0.2 part of benzoyl peroxide were fed into thesame reaction vessel as used in the preparation of the component (I).After the interior of the vessel was sufficiently substituted withnitrogen gas, the above-mentioned components were heated at 75° C. for 5hours to polymerize the monomers with stirring to obtain latexes havinga polymerization rate of 95%.

                                      TABLE 2                                     __________________________________________________________________________               (II)-1                                                                            (II)-2                                                                            (II)-3                                                                            (II)-4                                                                            (II)'-1                                                                           (II)'-2                                                                           (II)'-3                                    __________________________________________________________________________    Styrene    60  70  61  61  60  100 20                                         Ethyl acrylate                                                                           40  0   20   0  40  0   40                                         Butyl acrylate                                                                           0   30   0  20  0   0    0                                         Methyl methacrylate                                                                      0   0   19   0  0   0    0                                         Acrylonitrile                                                                            0   0    0  19  0   0   40                                         Triallyl cyanurate                                                                       2   2    2   2  0   2    2                                         __________________________________________________________________________

Measurement by the light transmission method indicated that particles inthe thus obtained latexes possessed particle diameters of 0.3 to 0.4μ.Powdery crosslinked polymers were obtained from the above latexesthrough the same procedure as employed for the preparation of thecomponent (I).

(3) Preparation of the resin (A₁)

Polymers (I)-1 to (I)-4 and polymers (II)-1 to (II)-4 or (II)'-1 to(II)'-3 were mixed together at ratios shown in Table 3 to prepare theresins (A₁). The resins (A₁) were added each in an amount of 7 parts to100 parts of the blend (1) of thermoplastic resin (B) with severaladditives, and composition of said blend (1) will be mentioned below.The mixture was kneaded by a roll at 165° C. to obtain a sheet. Thesheet was measured for its 60° specular gloss. Further, several piecesof the sheet were superposed and were compression-molded at 165° C.under a pressure of 40 kg/cm², to prepare a board 5 mm in thickness. Theboard was measured for its V-notched Charpy impact strength. Themeasured results were as shown in Table 3.

Table 3 also illustrates the measured results when no delustering agentwas added, when a silica gel was added as a representative example ofthe inorganic delustering agent, and when a commercially available highmolecular delustering agent was added.

As will be obvious from Table 3, the compositions of the presentinvention exhibit superior delustering property and impact resistance tothe compositions of comparative examples.

                                      TABLE 3                                     __________________________________________________________________________                                                 60°                                                                         Charpy                                                                   Specular                                                                           impact                      Resin                                        gloss                                                                              strength                    blended                                                                            (I)-1                                                                            (I)-2                                                                            (I)-3                                                                            (I)-4                                                                            (II)-1                                                                            (II)-2                                                                            (II)-3                                                                            (II)-4                                                                            (II)'-1                                                                           (II)'-2                                                                           (II)'-3                                                                           (%)  (kg-cm/cm.sup.2)                                                                     Remarks              __________________________________________________________________________    Resin                                                                              50          50                          23   15.9   Present              (A.sub.1)-1                                              invention            Resin   50       50                          28   17.2   Present              (A.sub.1)-2                                              invention            Resin      50    50                          24   15.1   Present              (A.sub.1)-3                                              invention            Resin         50 50                          27   16.3   Present              (A.sub.1)-4                                              invention            Resin   50           50                      31   17.5   Present              (A.sub.1)-5                                              invention            Resin   50               50                  24   16.8   Present              (A.sub.1)-6                                              invention            Resin   50                   50              26   16.5   Present              (A.sub.1)-7                                              invention            Resin   70       30                          35   18.6   Present              (A.sub.1)-8                                              invention            Resin   30       70                          21   14.5   Present              (A.sub.1)-9                                              invention            Resin   50                       50          65   18.9   Compara-             (A.sub.1 )'-1                        50                  tive                                                                          example              Resin   50                                   Poorly                                                                             8.9    Compara-             (A.sub.1)'-2                                 dispersed   tive                                                                          example              Resin   50                               50  Poorly                                                                             8.2    Compara-             (A.sub.1)'-3                                 dispersed   tive                                                                          example              Resin   100                                  75   20.5   Compara-             (A.sub.1)'-4                                             tive                                                                          example              Resin            100                         Poorly                                                                             7.8    Compara-             (A.sub.1)'-5                                 dispersed   tive                                                                          example              Resin                                                                              Silica gel                              46   0.8    Compara-             (A.sub.1)'-6                                             tive                                                                          example              Resin                                                                              Commercially available delustering agent                                                                              40   10.5   Compara-             (A.sub.1)'-7                                             tive                                                                          example              Resin                                                                              None                                    81   20.9   Compara-             (A.sub.1)'-8                                             tive                                                                          example              __________________________________________________________________________

    ______________________________________                                        Composition of blend (1):                                                     ______________________________________                                        Vinyl chloride resin (--P= 700)                                                                         100    parts                                        Stabilizer (dibutyltin maleate)                                                                         3      parts                                        Impact resistance aid     10     parts                                        (Metablen ® C-102, Mitsubishi Rayon Co.)                                  Processing aid (Metablen ® P-551,                                                                   1      part                                         Mitsubishi Rayon Co.)                                                         Lubricant (butyl stearate)                                                                              1      part                                         ______________________________________                                    

EXAMPLE 2

250 Parts of water, monomers of the first stage in parts as shown inTable 4, 1 part of sodium N-lauroyl sarcosinate and 0.3 part ofpotassium persulfate were introduced into the same reaction vessel asused for the preparation of the component (I) of Example 1. After theinterior of the vessel was sufficiently substituted with nitrogen, theabove-mentioned components were heated at 75° C. for 2 hours topolymerize the monomers with stirring. Thereafter, monomers of thesecond stage and polymerization regulator in parts as shown in Table 4and 0.2 part of benzoyl peroxide were introduced into the vessel toperform the polymerization for 5 hours. Latexes were obtained having apolymerization rate of 96% and an average particle size of 0.35μ.

The resins (A₂) and (A₃) were obtained from the thus prepared latexes inthe same manner as the preparation of the component (I) of Example 1.Further, the resin (A₂) or (A₃) was added each in an amount of 7 partsto 100 parts of the blend (1). The 60° specular gloss and Charpy impactstrength of the resulting compositions were measured in the same manneras in Example 1. The results were as shown in Table 4.

The compositions of the present invention exhibit excellent delusteringproperty and impact resistance over the compositions of comparativeexamples.

                                      TABLE 4                                     __________________________________________________________________________    First-stage                     Second-stage                                  monomer                         monomer                                              Methyl              Allyl               Methyl     Allyl                      methac-                                                                            Butyl                                                                              Ethyl     methac-   Ethyl                                                                              Butyl                                                                              methac-                                                                            Acryloni-                                                                           methac-                    rylate                                                                             acrylate                                                                           acrylate                                                                           Styrene                                                                            rylate                                                                             Styrene                                                                            acrylate                                                                           acrylate                                                                           rylate                                                                             trile rylate              __________________________________________________________________________    Resin (A.sub.2)-1                                                                    27    3                  42   28                   2                   Resin (A.sub.2)-2                                                                    45    5                  30        20              1.5                 Resin (A.sub.2)-3                                                                    40   10                  31   10         9         2                   Resin (A.sub.2)-4                                                                    48   12                  25    8             7     2                   Resin (A.sub.3)-1                                                                              28   42   2               3   27                             Resin (A.sub.3)-2                                                                     9        10   31   1              10   40         0.5                 Resin (A.sub.3)-3                                                                     9        10   31   2    30        20                                  Resin (A.sub.2)'-1                                                                   10   40                  30   20                   2                   Resin (A.sub.2)'-2                                                                   45    5                  30   20                   0                   Resin (A.sub.2)'-3                                                                   40   10                  10   20        20         2                   Resin (A.sub.3)'-1                                                                   20        20   10   2               5   45                             __________________________________________________________________________                                                60°                                                                         Charpy                                                             P.R.  Specular                                                                           impact                                                             t-dodecyl                                                                           gloss                                                                              strength                                                           mercaptan                                                                           %    (kg-cm/cm.sup.2)                                                                     Remarks               __________________________________________________________________________                                   Resin (A.sub.2)-1                                                                    0.05  27   17.5   Present                                                                       invention                                            Resin (A.sub.2)-2                                                                          25   17.3   Present                                                                       invention                                            Resin (A.sub.2)-3                                                                          23   16.5   Present                                                                       invention                                            Resin (A.sub.2)-4                                                                    0.03  24   16.7   Present                                                                       invention                                            Resin (A.sub.3)-1                                                                          28   16.8   Present                                                                       invention                                            Resin (A.sub.3)-2                                                                    0.07  21   15.9   Present                                                                       invention                                            Resin (A.sub.3)-3                                                                          26   16.3   Present                                                                       invention                                            Resin (A.sub.2)'-1                                                                         62   19.1   Comparative                                                                   Example                                              Resin (A.sub.2)'-2                                                                         71   20.3   Comparative                                                                   Example                                              Resin (A.sub.2)'-3                                                                         Poorly                                                                              7.7   Comparative                                                       dispersed   Example                                              Resin (A.sub.3)'-1                                                                         Poorly                                                                               9.5  Comparative                                                       dispersed   Example               __________________________________________________________________________     P.R.: Polymerization regulator                                           

EXAMPLE 3

250 Parts of water, 0.15 part of sodium N-lauroyl sarcosinate and 0.2part of sodium formaldehyde sulfoxylate were fed into a reaction vesselequipped with a stirrer and a reflux condenser.

After the interior of the vessel was sufficiently substituted withnitrogen, the above-mentioned components were heated to 75° C. withstirring.

Then, the monomer mixture of the first stage in parts as shown in Table5 and cumene hydroperoxide (0.1 part per 100 parts of monomers) wasadded to the reaction vessel over a period of 60 minutes and thereaction vessel was further agitated for 60 minutes to complete thefirst stage polymerization.

Before introducing the second stage monomers, the mixture of 10 parts ofwater, 0.6 part of sodium N-lauroyl sarcosinate and 0.1 part of sodiumformaldehyde sulfoxylate was added to the vessel, and then the monomermixture of the first stage in parts as shown in Table 5 which wascontained 0.2% of cumene hydroperoxide was added to the vessel over aperiod of 120 minutes and the vessel was further agitated for 180minutes to complete the second stage polymerization.

The latex having a polymerization rate of 96% and an average particlediameter of about 0.5μ was obtained.

The latex was salted out by the addition of 5 parts of calcium chloride,and was further dehydrated, washed with water and was dried to obtainpowdery polymer.

Further, the resin (A2) was blended in an amount of 7 parts to 100 partsof the blend (1'), and the obtained mixture was extrusion-molded toprepare a film 100μ in thickness.

The 60° specular glosses of the films are shown in Table 5.

    ______________________________________                                        Composition of blend (1):                                                     ______________________________________                                        Vinyl chloride resin (--P= 700)                                                                       100 parts                                             Dibutyltin maleate      3 parts                                               Impact resistance aid   10 parts                                              (Metablen ® C-102)                                                        Processing aid          1 part.sup.                                           (Metablen ® P-551)                                                        Lubricant               1.5 parts                                             ______________________________________                                    

                                      TABLE 5                                     __________________________________________________________________________           First-stage monomer   Second-stage monomer                                                                             60°                           Methyl                                   Specular                             methacry-                                                                           Butyl acry-                                                                         Ethyl             Butyl                                                                              Allyl gloss                                late  late  acrylate                                                                           Styrene                                                                            Ethyl acrylate                                                                        acrylate                                                                           acrylate                                                                            (%)                           __________________________________________________________________________    Resin (A.sub.2)-5                                                                    27     3         42           28   0.7   19                            Resin (A.sub.2)-6                                                                    40    10         30           20   1.0   23                            Resin (A.sub.2)-7                                                                    40          10   30   10      10   1.5   27                            __________________________________________________________________________

EXAMPLE 4

125 Parts of water, monomers of the first stage in parts as shown inTable 6, 0.2 part of benzoyl peroxide and 2 parts of sodium N-lauroylsarcosinate were introduced to the same reaction vessel as used inExample 1. After the interior of the vessel has been sufficientlyflushed with nitrogen, the above-mentioned components were heated at 75°C. to polymerize monomers until the polymerization rate reached 95%.

After the polymerization of the first stage was finished, sulfuric acidwas added in small amounts so that the latexes once assumed the creamystate. Thereafter, 125 parts of water, monomers of the second stage inparts as shown in Table 6, 1 part of polyvinyl alcohol, 1 part oflauroyl peroxide and 0.03 part of n-octyl mercaptan, were added toeffect the suspension polymerization at 80° C. for 2 hours withstirring, followed by the heat treatment at 120° C. for 30 minutes tocomplete the polymerization, and further followed by the dehydration anddrying to obtain granular polymer resins (A₂) and (A₃). The thusobtained resin (A₂) or (A₃) was added in an amount of 7 parts to 100parts of the blend (1) of the thermoplastic resin (B), in order tomeasure the 60° C. specular gloss and Charpy impact strength of thecompositions in the same manner as in Example 1. The results were asshown in Table 6.

The compositions of the present invention exhibited excellentdelustering property and impact resistance.

                                      TABLE 6                                     __________________________________________________________________________           First-stage monomer                                                                             Second-stage monomer      60°                                                                         Charpy                       Methyl            Allyl Methyl         Allyl                                                                              Specular                                                                           impact                       meth-                                                                              Butyl                                                                              Ethyl                                                                              Sty-                                                                             methy-                                                                              methy-                                                                             Ethyl     meth-                                                                              gloss                                                                              strength                     acrylate                                                                           acrylate                                                                           acrylate                                                                           rene                                                                             acrylate                                                                            acrylate                                                                           acrylate                                                                           Styrene                                                                            acrylate                                                                           (%)  (kg-cm/cm.sup.2)      __________________________________________________________________________    Resin (A.sub.2)-8                                                                    54   6                       16   24   1    22   16.5                  Resin (A.sub.3)-4                                                                     7   8         25 1.5   54   6              25   17.8                  Resin (A.sub.3)-5                                                                              24   36 2     40                  24   17.2                  __________________________________________________________________________

EXAMPLE 5

5 Parts of resins (A₁), (A₂) and (A₃) shown in Table 7, and 5 parts ofsilica gel or a commercially available delustering agent were blended tothe blend (2) of thermoplastic resin (B) with several additives(composition of said blend (2) will be mentioned below), and werekneaded by a roll heated at 155° C. to obtain sheets. The sheets weremeasured for their 60° specular gloss. The results were as shown inTable 7. From Table 7, it will be understood that the compositions ofthe present invention exhibit superior delustering effect to thecompositions of comparative examples.

    ______________________________________                                        Composition of blend (2):                                                     ______________________________________                                        Vinyl chloride resin (--P= 1100)                                                                       100 parts                                            Plasticizer (dioctyl phthalate)                                                                        50 parts                                             Cd--Ba type stabilizer   2.5 parts                                            Stearic acid             0.3 part.sup.                                        ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                                    60°                                                                    Specular                                                                             Uniformity of                                                          gloss (%)                                                                            dispersion Remarks                                         ______________________________________                                        Resin (A.sub.1)-2                                                                           36       G          Present                                                                       Invention                                   Resin (A.sub.2)-2                                                                           31       G          Present                                                                       Invention                                   Resin (A.sub.3)-1                                                                           33       G          Present                                                                       Invention                                   Resin (A.sub.3)-2                                                                           28       G          Present                                                                       Invention                                   Silica gel is used                                                                          52       P          Comparative                                                                   Examples                                    Commercially available                                                                      44       P          Comparative                                 delustering agent is used         Examples                                    No delustering agent                                                                        87       --         Comparative                                 is used.                          Examples                                    ______________________________________                                         G: Good, P: Poor                                                         

EXAMPLE 6

8 Parts of a resin (A₁), (A₂) and (A₃) shown in Table 8 or acommercially available delustering agent was added to 100 parts of anABS resin (Diapet® 3001, a product of Mitsubishi Rayon Co.) and wassufficiently mixed using a Henschel mixer. The mixture was extruded byan extruder hving a screw 40 mm in diameter at a temperature of 230° C.,and was cut to prepare pellets. The pellets were dried and wereinjection-molded at 200° C. to prepare a board 3 mm in thickness, tomeasure the 60° specular gloss and the V-notched Izod impact strength.The results were as shown in Table 8.

The compositions of the present invention exhibit excellent delusteringproperty and impact strength over the compositions of comparativeexamples.

                  TABLE 8                                                         ______________________________________                                                    60°                                                                           Izod impact                                                            Specular                                                                             strength                                                               gloss (%)                                                                            (kg-cm/cm.sup.2)                                                                         Remarks                                         ______________________________________                                        Resin (A.sub.1)-2                                                                           35       19.5       Present                                                                       Invention                                   Resin (A.sub.2)-2                                                                           38       20.4       Present                                                                       Invention                                   Resin (A.sub.3)-1                                                                           29       19.7       Present                                                                       Invention                                   Resin (A.sub.3)-2                                                                           34       21.5       Present                                                                       Invention                                   Commercially available                                                                      81        6.2       Comparative                                 delustering agent is used         Examples                                    No delustering agent                                                                        95       23.4       Comparative                                 is used.                          Examples                                    ______________________________________                                    

What is claimed as new and desired to be secured by Letters Patent ofthe United States is:
 1. A delustered thermoplastic resin composition,comprising:100 parts by weight of a thermoplastic resin (B) selectedfrom the group consisting of a vinyl chloride resin, an acrylic resin, amethacrylic resin, a nylon, a polyethylene, a polycarbonate, and apolyethylene terephthalate; and 0.1 to 40 parts by weight of a resin (A)which consists essentially of: 80 to 20 parts by weight of a polymer ora copolymer component (I) obtained by polymerizing;(a) 30 to 100% byweight of at least one alkyl methacrylate in which the alkyl group has 1to 4 carbon atoms; (b) 0 to 70% by weight of an alkyl acrylate in whichthe alkyl group has 1 to 13 carbon atoms; and (c) 0 to 50% by weight ofa monoethylenically unsaturated monomer other than those of (a) and (b);and 20 to 80 parts by weight of a copolymer component (II) obtained bypolymerizing;(d) 30 to 90% by weight of an aromatic vinyl compound; (e)10 to 60% by weight of at least one alkyl acrylate monomer in which thealkyl group has 1 to 13 carbon atoms; (f) 0 to 20% by weight of amonoethylenically unsaturated monomer other than those of (d) and (e);and (g) 0.05 to 10 parts by weight of a cross-linking monomer per 100parts by weight of the total amount of the above components (d), (e) and(f) said resin (A) being prepared by polymerizing the monomers whichconstitute copolymer (II) in the presence of the polymer or copolymercomponent (I).
 2. A delustered thermoplastic resin composition,comprising:100 parts by weight of a thermoplastic resin (B) selectedfrom the group consisting of a vinyl chloride resin, an acrylic resin, amethacrylic resin, a nylon, a polyethylene, a polycarbonate, and apolyethylene terephthalate; and 0.1 to 40 parts by weight of a resin (A)which consists essentially of: 80 to 20 parts by weight of a polymer ora copolymer component (I) obtained by polymerizing;(a) 30 to 100% byweight of at least one alkyl methacrylate in which the alkyl group has 1to 4 carbon atoms; (b) 20 to 70% by weight of an alkyl acrylate in whichthe alkyl group has 1 to 13 carbon atoms; and (c) 0 to 50% by weight ofa monoethylenically unsaturated monomer other than those of (a) and (b);and 20to 80 parts by weight of a copolymer component (II) obtained bypolymerizing;(d) 30 to 90% by weight of an aromatic vinyl compound; (e)10 to 60% by weight of at least one alkyl acrylate monomer in which thealkyl group has 1 to 13 carbon atoms; (f) 0 to 20% by weight of amonoethylenically unsaturated monomer other than those of (d) and (e);and (g) 0.05 to 10 parts by weight of a cross-linking monomer per 100parts by weight of the total amount of the above components (d), (e) and(f) said resin (A) being prepared by polymerizing the monomers whichconstitute copolymer component (II) in the presence of the polymer orcopolymer component (I).
 3. The composition of claim 1, wherein thecrosslinking monomer which constitutes the copolymer component (II) isat least one compound selected from the group consisting of allylmethacrylate, triallyl cyanurate and triallyl isocyanurate.
 4. Thecomposition of claim 1, wherein the resin (A) is in the granular formhaving an average particle diameter of greater than 0.3 micron.
 5. Thecomposition of claim 1 wherein in said composition, 100 parts by weightof said thermoplastic resin (B) is combined with up to 10 parts byweight of said resin (A).
 6. The composition of claim 1, wherein saidmonoethylenically unsaturated monomer in components I and II is fumaricacid, maleic acid, a carboxylic acid copolymerizable therewith or anester thereof, a halogenated vinyl compound, a vinyl ester oracrylonitrile.
 7. The composition of claim 1, wherein said compositionfurther comprises the addition of at least one additive thereto selectedfrom the group consisting of stabilizers, lubricants, processing aids,impact resistance aids, plasticizers, foaming agents, fillers, andcoloring agents.